JP3108403B2 - Photo-fixing composition and processing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide photographic light-sensitive material, which comprises processing with a processing solution containing at least one of a novel mercapto compound or a meso-ion thiolate compound. More specifically, the present invention relates to a bath containing a fixing agent even when the replenishment rate is reduced and a bath containing the fixing agent, and a method for processing a silver halide photographic light-sensitive material having excellent bath stability.

[0002]

2. Description of the Related Art Generally, processing of a silver halide color photographic light-sensitive material comprises a color developing process and a silver removing process. Silver generated by development is oxidized by a bleaching agent and then dissolved by a fixing agent. A ferric (III) ion complex salt (for example, aminopolycarboxylic acid-iron (III) complex salt) is mainly used as a bleaching agent, and a thiosulfate is generally used as a fixing agent. On the other hand, the processing of a black-and-white photographic light-sensitive material comprises a developing step and a step of removing unexposed silver halide, and unlike the processing of a color photographic light-sensitive material, fixing is performed without a bleaching step after development. Also in this case, thiosulfate is usually used as a fixing agent.

In recent years, as the replenishment rate has been reduced, a more stable liquid composition has been desired for each treatment bath. Regarding the fixing bath, thiosulfate, which is usually used, undergoes oxidative deterioration and is sulfurized to form a precipitate. Therefore, in most cases, sulfite is added as a preservative for preventing oxidation. However, as the replenishment is further reduced, the improvement of the liquid stability is further desired. It's gone.

On the other hand, from the viewpoint of speeding up, there is a demand for a compound having better fixability than thiosulfate. For these reasons, it has been desired to develop a fixing agent that replaces thiosulfate, which is excellent in oxidative stability and fixing property, but no good alternative compound has been found up to the present. Although many patents have been filed for antifoggants having improved sensitivity / fogging ratios, it has not been said that compounds having a sufficient antifogging effect have been found.

[0005]

Accordingly, a first object of the present invention is to provide a method for processing a silver halide photographic material which can be processed with a novel processing solution, which overcomes the above-mentioned disadvantages. A second object of the present invention is to provide a fixing method having excellent fixability. A third object of the present invention is to provide a bath containing a fixing agent even at a low replenishment amount, and a method for processing a silver halide photographic light-sensitive material having improved bath stability.

[0006]

The above object has been achieved by the following processing method and processing composition.

(1) In a processing method in which a silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support is exposed to light and then developed ,
At least one cationic group and at least one anion
At least one selected from a mercapto compound represented by the following general formula (I) having at least one cationic group and at least one anionic group at the same time as a substituent. A method for processing a silver halide photographic light-sensitive material, characterized by processing with a processing solution containing one compound. General formula (I)

[0008]

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(In the formula, Q represents an atomic group necessary for forming a tetrazole ring, a triazole ring, an imidazole ring or an oxadiazole ring. This heterocyclic ring is condensed with a carbon aromatic ring or a heteroaromatic ring. R represents an alkyl group, an alkenyl group, an aralkyl group, an aryl group or a heterocyclic group, n represents an integer of 1 to 4, and M represents a counter cation, provided that at least one of Rs is a cationic group. And (2) a process in which a silver halide photographic material having at least one photosensitive silver halide emulsion layer on a support is exposed and then developed. in the method, the bath having fixing ability is a minute
At least one cationic group and at least one
At least one selected from a mercapto compound represented by the following general formula (I) having an anionic group as a substituent at the same time and a meso-ion thiolate compound having at least one cationic group and at least one anionic group as a substituent in one molecule. A method for processing a silver halide photographic material, comprising one compound. General formula (I)

Embedded image (In the formula, Q represents an atom group necessary for forming a tetrazole ring, a triazole ring, an imidazole ring or an oxadiazole ring. This heterocycle may be condensed with a carbon aromatic ring or a heteroaromatic ring. R represents an alkyl group, an alkenyl group, an aralkyl group, an aryl group or a heterocyclic group, n represents an integer of 1 to 4, and M represents a counter cation, provided that at least one of Rs is a cationic group or an anionic group. (3) at least one cationic group in one molecule;
A mercapto compound represented by the following general formula (I) having at least one anion group as a substituent and a meso-ion thiolate compound having at least one cation group and at least one anion group as a substituent in one molecule. A photographic fixing composition comprising at least one selected compound. General formula (I)

Embedded image (In the formula, Q represents an atom group necessary for forming a tetrazole ring, a triazole ring, an imidazole ring or an oxadiazole ring. This heterocycle may be condensed with a carbon aromatic ring or a heteroaromatic ring. R represents an alkyl group, an alkenyl group, an aralkyl group, an aryl group or a heterocyclic group, n represents an integer of 1 to 4, and M represents a counter cation, provided that at least one of Rs is a cationic group or an anionic group. (4) A meso-ion thiolate compound having at least one cation group and at least one anion group as a substituent simultaneously in one molecule is represented by the general formula (II): 2. The method for processing a silver halide photographic material according to claim 1, which is a compound represented by the formula: General formula (II)

[0010]

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In the formula, Z represents an atom group necessary for forming a 5- or 6-membered mesoionic ring. This heterocyclic ring may be condensed with a carbon aromatic ring or a heteroaromatic ring. R has the same meaning as that of the formula (I). m represents an integer of 1 to 3.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Next, general formulas (I) and (II) used in the present invention will be described in detail. In the general formula (I), Q represents a tetrazole ring, a triazole ring,
A group of atoms necessary to form a dazole ring or an oxadiazole ring. The heterocyclic ring may be fused with a carbon aromatic ring or a heteroaromatic ring . R has 1 to 10 carbon atoms
(E.g., a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, a 2-hydroxypropyl group, a hexyl group, and an octyl group); , A butenyl group), an aralkyl group having 7 to 12 carbon atoms (eg, benzyl group, phenethyl group), an aryl group having 6 to 12 carbon atoms (eg, phenyl group, 2-chlorophenyl group, 3-methoxyphenyl group, naphthyl group), Represents a heterocyclic group having 1 to 10 carbon atoms (for example, pyridyl group, thienyl group, furyl group, triazolyl group, imidazolyl group).

R is a group obtained by arbitrarily combining the aforementioned alkyl group, alkenyl group, aralkyl group, aryl group and heterocyclic group (for example, a heterocyclic-substituted alkyl group).
It may be, -CO -, - CS -, - SO 2 -,
It may include a linking group obtained by optionally combining -O- or -S-. However, at least one of R is substituted with at least one of a cationic group and an anionic group.

As the cationic group, an amino group that becomes a cation by protonation (eg, an unsubstituted amino group, a dimethylamino group, a diethylamino group, an N-hydroxyethyl-N
-Methylamino group), ammonium group (for example, trimethylammonium group, triethylammonium group, dimethylbenzylammonium group, N-hydroxyethyl-
N, N-dimethylammonium group), phosphonium group (for example, trimethylphosphonium group, tributylphosphonium group), quaternary heterocyclic salt (for example, N-methylpiperidino group, pyridinium group) and the like.

Examples of the anionic group include a carboxylic acid or a salt thereof (eg, sodium salt, potassium salt, ammonium salt, calcium salt), a sulfonic acid or a salt thereof (eg, sodium salt, potassium salt, ammonium salt, magnesium salt, calcium salt), Phosphonic acid or a salt thereof (eg, a sodium salt, a potassium salt, an ammonium salt) and the like. Compounds having an anionic group and a cationic group in the same molecule, such as the compounds used in the present invention, are usually isolated as inner salts. The anion group and the cation group may be substituted by the same group, for example,

[0016]

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[0017] M represents a cation group (for example, an alkali metal atom such as a hydrogen atom, a sodium atom and a potassium atom, an alkaline earth metal atom such as a magnesium atom and a calcium atom, an ammonium group such as an ammonium group and a triethylammonium group).

The heterocyclic ring and R in the general formula (I)
Is a nitro group, a halogen atom (eg, a chlorine atom or a bromine atom), a mercapto group, a cyano group, a substituted or unsubstituted alkyl group (eg, a methyl group, an ethyl group, a propyl group, a t-butyl group, a cyanoethyl group), Aryl group (for example, phenyl group, 4-methanesulfonamidophenyl group, 4-methylphenyl group, 3,4-dichlorophenyl group, naphthyl group), alkenyl group (for example, allyl group), aralkyl group (for example, benzyl group, 4 -Methylbenzyl group, phenethyl group), sulfonyl group (for example, methanesulfonyl group, ethanesulfonyl group, p-toluenesulfonyl group), carbamoyl group (for example, unsubstituted carbamoyl group, methylcarbamoyl group, phenylcarbamoyl group), sulfamoyl group (for example, Unsubstituted sulfamoyl group, methyl sulfamo Group, phenylsulfamoyl group), carbonamido group (eg, acetamido group, benzamide group), sulfonamido group (eg, methanesulfonamido group, benzenesulfonamido group, p-toluenesulfonamido group), acyloxy group (eg, acetyl Oxy group, benzoyloxy group), sulfonyloxy group (for example, methanesulfonyloxy group), ureido group (for example, unsubstituted ureido group, methylureide group, ethylureide group, phenylureide group), thioureido group (for example, unsubstituted thioureide group) , Methylthioureido group),
Acyl groups (eg, acetyl group, benzoyl group), oxycarbonyl groups (eg, methoxycarbonyl group, phenoxycarbonyl group), oxycarbonylamino groups (eg, methoxycarbonylamino group, phenoxycarbonylamino group, 2-ethylhexyloxycarbonylamino group), It may be substituted with a hydroxyl group or the like.

N represents an integer of 1 to 4. When n represents 2 or 3, each R may be the same or different. In the general formula (I), R preferably has 1 to 1 carbon atoms.
4 represents an alkyl group or an aryl group having 6 to 10 carbon atoms, a cation group substituted with R represents an amino group or an ammonium group, and an anion group represents a carboxylic acid or a salt thereof, a sulfonic acid or a salt thereof, n represents 1 or 2.

Next, the general formula (II) will be described in detail. In the general formula (II), Z represents a 5- or 6-membered mesoionic ring composed of a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom or a selenium atom. m represents an integer of 1 to 3, and R has the same meaning as in formula (I).

The mesoionic compound represented by the general formula (II) of the present invention is a quarterly W.Baker and WDOllis.
Reviews (Ouart. Rev.) 11, 15 (1957), Advances in Heterocyclic Chemistry 19, 1 (19)
76) is a group of compounds defined as "5- or 6-membered heterocyclic compound, which cannot be satisfactorily represented by one covalent structural formula or polar structural formula, and all atoms constituting the ring Compounds having a pi-electron hexaploid associated with are associated with a partial positive charge and are balanced with an equal negative charge on the exocyclic atom or group. "

The mesoionic ring represented by Z includes an imidazolium ring, a pyrazolium ring, an oxazolium ring, a thiazolium ring, a triazolium ring, a tetrazolium ring,
Thiadiazolium ring, oxadiazolium ring, thiatriazolium ring, oxatriazolium ring and the like. m represents an integer of 1 to 3, and R has the same meaning as in formula (I). Further, the mesoionic ring represented by Z and R may be substituted with the substituents described in formula (I).

In the general formula (II), preferably Z is an imidazolium ring, 1,2,4-triazolium ring, 1,2,3-
Represents a triazolium ring, R represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms, a cation group substituted with R represents an amino group or an ammonium group, and an anion group represents a carboxylic acid or a carboxylic acid thereof. Represents a salt, a sulfonic acid or a salt thereof, and n represents 1 or 2. Hereinafter, specific examples of the compound that can be used in the present invention are shown, but the invention is not limited thereto.

[0024]

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[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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The compound of the general formula (I) used in the present invention is a compound represented by Berichte der Deutschen Chemischen Ge
sellschaft) 28, 77 (1895), JP-A-50-3
Nos. 7436 and 51-3231, U.S. Pat.
5,976; U.S. Pat. No. 3,376,310; Berichte der Deutschen Chemischen Gesellschaf
t) 22, 568 (1889), 29, 2483 (1
896), Journal of Chemical Society (J. Chem. Soc.) 1932, 1806, Journal of the American Chemical Society (JA).
m. Chem. Soc.) 71, 4000 (1949); U.S. Pat. Nos. 2,585,388 and 2,541,924; Advances in Heterocyclic Chemistry 9,165.
(1968), Organic Synthesis (Organic Sy)
nthesis) IV, 569 (1963), Journal of
The American Chemical Society (J. Am.
Chem. Soc.) 45, 2390 (1923), Hemiche
Berichte (Chemische Berichte) 9, 465 (187
6), JP-B-40-28496, JP-A-50-890
No. 34, U.S. Pat. Nos. 3,106,467 and 3,42.
0,670, 2,271,229, 3,13
7,578, 3,148,066, 3,51
No. 1,663, No. 3,060,028, No. 3,27
Nos. 1,154, 3,251,691, 3,59
8,599, 3,148,066, JP-B-43-
No. 4135, U.S. Pat. Nos. 3,615,616 and 3,4
20,664, 3,071,465, 2,44
No. 4,605, No. 2,444,606, No. 2,44
No. 4,607, 2,935,404 and the following synthesis examples.

The compounds of the general formula (II) of the present invention can be prepared by the methods described in Journal of Heterocyclic Chemistry (J. Heterocyclic Chem.) 2, 105 (1965) and Journal of Organic Chemistry (J. Org). .
Chem.) 32, 2245 (1967), Journal of Chemical Society (J. Chem. Soc.) 3799 (1
969), Journal of American Chemical
Society (J. Am. Chem. Soc.) 80, 1895 (19
58), Chemical Communication (Chem.Commu)
n.) 1222 (1971); Tetrahedron Lett. 2939 (1972);
No. 0-87322, Berichte der Deutschen
Chemischen Gesellschaft) 38, 4049 (190
5), Journal of Chemical Society Chemical Communication (J.Chem.Soc.Chem.Commu)
n.) 1224 (1971), JP-A-60-122936
No., JP-A-60-117240, Advances in Heterocyclic Chemistry (Advances in
Heterocyclic Chemistry) 19, 1 (1976), Tetrahedron Letters 5881
(1968), Journal of Heterocyclic Chem. (J. Heterocyclic Chem.) 5, 277
(1968), Journal of Chemical Society, Perkin Transaction I (J. Chem. Soc., Pe
rkin Trans. I) 627 (1974), Tetrahedron Letters 1809 (196)
7), 1578 (1971), Journal of Chemical Society (J. Chem. Soc.) 899 (193)
5), 2865 (1959), Journal of Organic Chemistry (J. Org. Chem.) 30, 567.
(1965) and the following synthesis examples.

[0033]

Synthesis Example 1 (Synthesis of Exemplified Compound 1) N, N-dimethyl-N-isothiocyanatoethyl-N-
A solution prepared by dissolving 6.5 g of sodium azide in 100 ml of water was added to 25.2 g of the sulfopropylammonium inner salt, and the mixture was refluxed for 4 hours under a nitrogen atmosphere. After the reaction, 8.6 ml of concentrated hydrochloric acid was added to the reaction solution for neutralization, and then the precipitate was filtered and the filtrate obtained was dried under reduced pressure. The obtained solid was subjected to silica gel chromatography (eluent: chloroform / methanol = 3 /
The product was purified in 1) and recrystallized from a mixed solvent of 100 ml of methanol and 10 ml of water to obtain 7.1 g (yield: 24%) of the desired product.
( Melting point 300 ° C. or higher ). The obtained crystal was confirmed to be the target substance by NMR, mass spectrum and elemental analysis.

Synthesis Example 2 (Synthesis of Exemplified Compound 34) N, N-dimethyl-N-isothiocyanatoethyl-N-
20.2 g of sulfopropylammonium inner salt was dissolved in 200 ml of acetonitrile, 7.0 g of 1-acetyl-1-methylhydrazine was added, and the mixture was heated under reflux for 3 hours. After the reaction, the reaction solution was cooled to room temperature, and sodium methoxide 28%
16.4 ml of a methanol solution was added, and the mixture was stirred at room temperature for 1 hour. After the reaction, the precipitated crystals were filtered and recrystallized from 80 ml of methanol to obtain 10.3 g (yield: 40%) of the desired product.
( Mp 289-91 ° C ). The obtained crystal was confirmed to be the target substance by NMR, mass spectrum and elemental analysis.

The compounds used in the present invention can be used, for example, in an image forming method using a silver halide photographic light-sensitive material. Specifically, it is useful as a silver halide solvent at the time of grain formation, as an additive for improving the sensitivity / fogging ratio, and as a fixing agent in a developing method.

When the above compound used in the present invention is contained in a silver halide photographic light-sensitive material, the content is preferably 0.001 to 20 g, and more preferably 0.01 to 20 g per mol of silver halide.
1-5 g is preferred.

When the above-mentioned compound used in the present invention is used for forming silver halide grains, the conditions of the physical ripening step, for example, pH, pAg, temperature, time and additives are not particularly limited, and are generally used in the art. It can be performed under the conditions that have been set. For example, the pH value is preferably from 3.0 to 8.5, particularly preferably from 5.0 to 7.5, and the pAg value is preferably 7.0 or more.
To 9.5, especially 8.0 to 9.3, and the temperature is preferably 40 to 85 ° C, particularly preferably 45 to 75 ° C, and the time is preferably 10 to 200 minutes, particularly preferably 30 to 120 minutes. The addition amount is from 0.001 to 2 per mol of silver halide.
0 g, especially 0.01 to 10 g, is preferred.

When the above compound used in the present invention is added to a processing solution (for example, a developing solution, a fixing solution, a bleaching solution, or a washing water), the amount added is preferably 1 × 10 ^-4 to 10 mol / l. And more preferably 1 × 10 ^{−3 to} 5 mol / l, particularly preferably 1 × 10 ^{−3 to} 3 mol / l. When the compound of the present invention is added to a solution having a fixing ability (for example, a fixing solution or a bleach-fixing solution), it is less susceptible to oxidative deterioration than thiosulfuric acid which is a conventionally used fixing agent, and has an excellent fixing ability. Can be pulled out greatly.

The amount of the compound used in the present invention used in the fixing bath is preferably from 1 × 10 ⁻⁴ to 10 mol / l, more preferably from 1 × 10 ^{−3 to} 5 mol / l. It is 1 × 10 ^{-2 to} 3 mol / l. Or the amount used in the bleach-fix bath is 2 × 10 ^-2 to 1
0 mol / l is appropriate, and 2 × 10 ^{-1 to} 3 mol / ^l
Liters are preferred. Here, when the halogen composition of the silver halide emulsion in the light-sensitive material to be processed is AgBrI (I ≧ 2 mol% or more), the silver halide emulsion is preferably used at 0.5 to 2 mol / l, more preferably 1.2 mol / l. ２2 mol / liter. When the halogen composition is AgBr or AgBrC
In the case of 1 or high silver chloride (AgCl ≧ 80 mol%), it is preferable to use 2 × 10 ⁻¹ to 1 mol / l.

The sensitivity / fogging ratio can be improved by incorporating the above compound used in the present invention into a silver halide light-sensitive material. / W shooting film,
Black and white photosensitive materials such as black and white photographic paper, infrared photosensitive materials for laser scanners, color papers, color reversal papers, color negative films for photography, color reversal films,
Examples thereof include color photographic materials such as color negative films or color positive films for movies, and transmission type or reflection type direct positive photographic materials. Further, the present invention can also be applied to a silver salt diffusion transfer photosensitive material, a color diffusion photosensitive material, a heat developed color photosensitive material, and the like.

Next, a silver halide color photographic light-sensitive material and a processing method using the same will be described in detail. However,
Matters common to black and white photosensitive materials are also described. The silver halide color photographic light-sensitive material that can be processed by the method of the present invention is provided with at least one of a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer on a support. The number and order of the silver halide emulsion layers and the non-photosensitive layers are not particularly limited. Typically, at least one light-sensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities is provided on a support.
A silver halide photographic light-sensitive material, wherein the photosensitive layer is a unit light-sensitive layer having color sensitivity to any of blue light, green light and red light, In general, the arrangement of the unit photosensitive layers is arranged in the order of a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer from the support side. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between layers of the same color sensitivity.

Non-light-sensitive layers such as various intermediate layers may be provided between the silver halide light-sensitive layers and as the uppermost layer and the lowermost layer. The intermediate layer is described in JP-A-61-43748,
Nos. 9-113438, 59-113440, 61
Couplers, DIR compounds and the like described in JP-A-20037 and JP-A-61-20038, and may contain a color mixture inhibitor as usually used. As described in West German Patent No. 1,121,470 or British Patent No. 923,045, a plurality of silver halide emulsion layers constituting each unit photosensitive layer may be composed of a high-speed emulsion layer and a low-speed emulsion layer. A two-layer configuration can be preferably used. Usually, it is preferable to arrange them so that the light sensitivity decreases sequentially toward the support, and a non-photosensitive layer may be provided between the respective halogen emulsion layers. Also, JP-A-57-112751, JP-A-62-200350 and JP-A-6-200350
A low-speed emulsion layer on the side away from the support as described in JP-A-2-206541 and JP-A-62-206543;
A high-sensitivity emulsion layer may be provided on the side close to the support.

As a specific example, from the side farthest from the support,
Low-sensitivity blue-sensitive layer (BL) / High-sensitivity blue-sensitive layer (BH)
/ High sensitivity green photosensitive layer (GH) / Low sensitivity green photosensitive layer (G
L) / high-sensitivity red-sensitive layer (RH) / low-sensitivity red-sensitive layer (RL), or BH / BL / GL / GH / RH /
RL order or BH / BL / GH / GL / RL / RH
And so on. In addition, Japanese Patent Publication No. 55-34
As described in Japanese Patent No. 932, it is also possible to arrange in the order of blue-sensitive layer / GH / RH / GL / RL from the farthest side from the support. Japanese Patent Application Laid-Open No. 56-25738
And the blue-sensitive layer / GL / RL from the side farthest from the support as described in JP-A-62-63936.
The sequence may be arranged in the order of / GH / RH.

Further, as described in JP-B-49-15495, the upper layer is the silver halide emulsion layer having the highest sensitivity, the middle layer is the silver halide emulsion layer having a lower sensitivity, and the lower layer is the middle layer. Further, an arrangement is also possible in which a silver halide emulsion layer having a lower sensitivity is further disposed, and an arrangement is formed of three layers having different sensitivities in which the sensitivities are successively decreased toward the support. Even in the case of three layers having different sensitivities, as described in JP-A-59-202264, a medium-sensitivity emulsion from the side farther from the support in the same color-sensitive layer. Layers / high-speed emulsion layers / low-speed emulsion layers. As described above, various layer configurations and arrangements can be selected according to the purpose of each photosensitive material. When the silver halide color photographic material is a color negative film or a color reversal film, preferred silver halide contained in the photographic emulsion layer is silver iodobromide containing about 30 mol% or less of silver iodide, It is silver iodochloride or silver iodochlorobromide. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 25 mol% of silver iodide.

When the silver halide color photographic light-sensitive material is color photographic paper, the silver halide contained in the photographic emulsion layer may be silver chlorobromide or silver chloride containing substantially no silver iodide. Can be preferably used. Here, "contains substantially no silver iodide" means that the silver iodide content is 1 mol% or less, preferably 0.2 mol% or less. Regarding the halogen composition of these silver chlorobromide emulsions, any silver bromide / silver chloride emulsion can be used. Although this ratio can take a wide range depending on the purpose, a silver chloride ratio of 2 mol% or more can be preferably used. A so-called high silver chloride emulsion having a high silver chloride content is preferably used as a light-sensitive material suitable for rapid processing. The silver chloride content of these high silver chloride emulsions is preferably at least 90 mol%, more preferably at least 95 mol%. For the purpose of reducing the replenishment amount of the developing solution, the silver chloride content is 98 to 99.9.
Emulsions of almost pure silver chloride, such as mol%, are also preferably used.

The silver halide grains in the photographic emulsion include those having regular crystals such as cubic, octahedral and tetradecahedral, those having irregular crystal forms such as spherical and plate-like,
It may have a crystal defect such as a twin plane or a composite form thereof. The silver halide may be fine grains having a grain size of about 0.2 μm or less or large grains having a projected area diameter of about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion. The silver halide photographic emulsion that can be used in the present invention is, for example, Research Disclosure (hereinafter referred to as RD).
No. 17643 (December 1978), pp. 22-23,
“I. Emulsion preparation and types
No. 18716 (November 1979), 6
It can be prepared using the method described on page 48 and the like. U.S. Pat. Nos. 3,574,628 and 3,653
Monodisperse emulsions described in US Pat. No. 5,394 and British Patent No. 1,413,748 are also preferable.

Further, tabular grains having an aspect ratio of about 5 or more can be used in the present invention. Tabular grains are described by Gatoff, Photographic Science and Engineering.
gineering), Vol. 14, pp. 248-257 (1970)
U.S. Pat. Nos. 4,434,226 and 4,41.
No. 4,310, No. 4,433,048, No. 4,43
No. 9,520 and British Patent No. 2,112,157 can be easily prepared. The crystal structure may be uniform, the inside and the outside may be composed of different halogen compositions, may have a layered structure, and even if silver halides having different compositions are joined by epitaxial junction. Also, it may be bonded to a compound other than silver halide such as, for example, silver rhodan or lead oxide. Also, a mixture of particles of various crystal forms may be used.

As the silver halide emulsion, usually, those subjected to physical ripening, chemical sensitization and spectral sensitization are used. In the process of physical ripening, various polyvalent metal ion impurities (such as salts or complex salts of cadmium, zinc, lead, copper, thallium, iron, ruthenium, rhodium, palladium, osmium, iridium, platinum, etc.) can also be introduced. . Compounds used for chemical sensitization are described in JP-A-62-21.
No. 5,272, page 18, lower right column to page 22, upper right column. The additives used in such a process are RD No. 17643 and RD No. 187.
16 and the corresponding locations are summarized in the table below. Known photographic additives which can be used in the present invention are also described in the above two RDs, and the relevant portions are shown in the following table.

Additive type RD17643 RD18716 1 Chemical sensitizer page 23, page 648, right column 2 Sensitivity enhancer Same as above 3 Spectral sensitizer, page 23-24, page 648 right column to supersensitizer 649, right column 4 Brightener page 24 5 Antifoggant page 24-25 page 649 right column and stabilizer 6 light absorber, page 25-26 page 649 right column filter dye, page 650 left column UV absorber 7 stain inhibitor 25 Page right column 650 Page left to right column 8 Dye image stabilizer 25 Page 9 Hardener 26 Page 651 Left column 10 Binder 26 Same as above 11 Plasticizer, lubricant 27 Page 650 Right column 12 Coating aid, 26 Page to page 27 page 650 right column surfactant 13 static inhibitor page 27 same as above

Further, in order to prevent deterioration of photographic performance due to formaldehyde gas, US Pat.
It is preferable to add a compound capable of reacting with formaldehyde described in JP-A Nos. 7 and 4,435,503 to the light-sensitive material. Various color couplers can be used in the present invention, and specific examples thereof are described in RD No.
17643, VII-CG.

As the yellow coupler, for example, US Pat. Nos. 3,933,501 and 4,022,620;
Nos. 4,326,024, 4,401,752, 4,248,961, Japanese Patent Publication No. 58-10739, British Patent Nos. 1,425,020, and 1,476,760.
No. 3,973,968, U.S. Pat.
Nos. 023 and 4,511,649, European Patent No. 24
What is described in 9,473A etc. is preferable.

As the magenta coupler, 5-pyrazolone and pyrazoloazole compounds are preferable. US Pat.
European Patent No. 73,636, US Patent No. 3,061,4
No. 32, No. 3,725,064, RD No. 24220
(June 1984), JP-A-60-33552, RD
No. 24230 (June 1984), JP-A-60-43
No. 659, No. 61-72238, No. 60-35730
No. 55-118034, No. 60-185951
No. 4,500,630, U.S. Pat.
654, 4,556,630, WO (PCT) 8
What is described in 8/04795 etc. is especially preferable.

Examples of the cyan coupler include phenol type and naphthol type couplers.
52,212, 4,146,396, 4,22
8,233, 4,296,200, 2,36
9,929, 2,801,171, 2,77
2,162, 2,895,826, 3,77
2,002, 3,758,308, 4,33
4,011, 4,327,173, West German Patent Publication No. 3,329,729, European Patent No. 121,365A.
No. 249,453A, U.S. Pat.
No. 22, 4,333, 999, 4, 753, 87
No. 1, No. 4,451,559, No. 4,427,767
Nos. 4,690,889 and 4,254,212
No. 4,296,199, JP-A-61-42658.
And the like are preferred.

Colored couplers for correcting unnecessary absorption of coloring dyes are described in RD No. 17643, Sections VII-G,
U.S. Pat. No. 4,163,670, JP-B-57-394.
No. 13, U.S. Pat. Nos. 4,004,929 and 4,13
8,258 and British Patent No. 1,146,368 are preferred. No. 4,774,18.
A coupler for correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in No. 1, or a dye precursor capable of forming a dye by reacting with a developing agent described in US Pat. No. 4,777,120. It is preferable to use a coupler having a group as a leaving group.

Examples of couplers in which a coloring dye has an appropriate diffusibility include US Pat. No. 4,366,237, British Patent No. 2,125,570, and European Patent No. 96,570.
Those described in West German Patent (Published) No. 3,234,533 are preferred. Typical examples of polymerized dye-forming couplers are described in U.S. Pat.
0,211, 4,367,282, 4,40
9,320, 4,576,910, British Patent 2,
102, 173 and the like.

Couplers which release a photographically useful residue upon coupling can also be preferably used in the present invention. The DIR coupler releasing the development inhibitor is the same as described above for R
D17643, Patents described in VII to F, JP-A-5
Nos. 7-151944, 57-154234, 60
Nos. 184248, 63-37346, U.S. Pat. Nos. 4,248,962 and 4,782,012 are preferred. Examples of couplers which release a nucleating agent or a development accelerator imagewise during development include British Patent Nos. 2,097,140 and 2,131,188, JP-A-59-157538 and JP-A-59-170840. Are preferred.

Other couplers usable in the light-sensitive material usable in the present invention include those described in US Pat.
No. 4,427, and the like, U.S. Pat.
No. 283,472, No. 4,338,393, No. 4,3
Multi-equivalent couplers described in JP-A-10,618, etc.
185950, JP-A-62-24252, etc., DIR redox compound releasing couplers, DIR coupler releasing couplers, DIR coupler releasing redox compounds or DIR redox releasing redox compounds, after withdrawal described in EP 173,302A Couplers which release dyes for recoloring, RD Nos. 11449 and 2424
1. Bleaching accelerator releasing couplers described in JP-A-61-201247, ligand releasing couplers described in U.S. Pat. No. 4,553,477, and leuco dyes described in JP-A-63-75747 are released. Couplers which emit fluorescent dyes described in U.S. Pat. No. 4,774,181, and the like.

The coupler used in the present invention can be introduced into a light-sensitive material by various known dispersion methods. Examples of high boiling solvents used in the oil-in-water dispersion method are described in US Pat.
No. 027 and the like. Specific examples of the high boiling organic solvent having a boiling point at normal pressure of 175 ° C. or higher used in the oil-in-water dispersion method include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-cyclohexyl phthalate). 2-ethylhexyl phthalate, decyl phthalate, bis (2,4-
Di-t-amylphenyl) phthalate, bis (2,4-
Di-t-amylphenyl) isophthalate, bis (1,
Esters of phosphoric acid or phosphonic acid (triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxy) Ethyl phosphate,
Trichloropropyl phosphate, di-2-ethylhexylphenylphosphonate, etc.), benzoic esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides (N, N-diethyldodecaneamide, N , N-diethyllaurylamide, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4-di-tert-
Amyl phenols, etc.), aliphatic carboxylic acid esters (bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N, N-dibutyl-2) -Butoxy-5-t
tert-octylaniline and the like, and hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene and the like) and the like. As the auxiliary solvent, an organic solvent having a boiling point of about 30 ° C. or more, preferably 50 ° C. or more and about 160 ° C. or less can be used.
Butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide and the like.

The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in US Pat. No. 4,199,3.
No. 63, West German Patent Application (OLS) No. 2,541,274
And No. 2,541,230.
Further, these couplers are impregnated with a loadable latex polymer (for example, U.S. Pat. No. 4,203,716) in the presence or absence of the high-boiling organic solvent,
Alternatively, it can be dissolved in a water-insoluble and organic solvent-soluble polymer and emulsified and dispersed in a hydrophilic colloid aqueous solution. Preferably, homopolymers or copolymers described on pages 12 to 30 of International Publication No. WO88 / 00723 are used. In particular, use of an acrylamide-based polymer is preferred for stabilizing a color image. Suitable supports that can be used in the present invention are described in, for example, RD. No. 17643
No. 18716, and from page 647, right column, No. 18716
It is described in the left column on page 48.

The light-sensitive material used in the present invention has a total thickness of all hydrophilic colloid layers on the side having an emulsion layer of 25 μm or less, preferably 20 μm or less, and a film swelling speed T
_1/2 is preferably 30 seconds or less (preferably 15 seconds or less). The film thickness means a film thickness measured under humidity control at 25 ° C. and a relative humidity of 55% (2 days), and the film swelling rate T _1/2 can be measured according to a method known in the art.
For example, Photographic Science and Engineering (Phosphorus) by A. Green et al.
togr.Sci.Eng.), 19 vol., No. 2, can be measured by using the type of Swellometer described (swelling meter) pp 124-129, T _1/2 is 30 ° C. with a color developer, 90% of the maximum swollen film thickness reached when the treatment is performed for 3 minutes and 15 seconds is defined as a saturated film thickness, and is defined as a time until the film thickness reaches 1/2 of the saturated film thickness. The film swelling speed T _1/2 can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating. The swelling ratio is preferably from 150 to 400%. The swelling ratio can be calculated from the maximum swelling film thickness under the conditions described above according to the formula: (maximum swelling film thickness-film thickness) / film thickness.

The above-mentioned color photographic light-sensitive material is made of the above-mentioned RD
No. 17643, pp. 28-29, and No. 18716
615 can be developed by the usual method described in the left column to the right column. The color developing solution used for developing the photosensitive material is preferably an alkaline aqueous solution mainly containing an aromatic primary amine-based color developing agent. Aminophenol compounds are also useful as the color developing agent, but p-phenylenediamine compounds are preferably used, and typical examples thereof include 3-methyl-4-amino-N, N-diethylaniline and 3-methyl -4-amino-
N-ethyl-N-β-hydroxyethylaniline, 3-
Methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-
N-ethyl-β-methoxyethylaniline and sulfates, hydrochlorides or p-toluenesulfonates thereof are exemplified. These compounds can be used in combination of two or more depending on the purpose.

The color developing solution may be a pH buffer such as a carbonate, borate or phosphate of an alkali metal, a development inhibitor such as a bromide salt, an iodide salt, a benzimidazole, a benzothiazole or a mercapto compound. It generally contains an agent or an antifoggant. If necessary, such as hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenylsemicarbazide, triethanolamine, catecholsulfonic acid, and triethylenediamine (1,4-diazabicyclo [2,2,2] octane) Various preservatives, organic solvents such as ethylene glycol and diethylene glycol, development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts and amines, dye-forming couplers, competitive couplers, fogging agents such as sodium boron hydride , An auxiliary developing agent such as 1-phenyl-3-pyrazolidone, a viscosity-imparting agent, various chelating agents represented by aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid and phosphonocarboxylic acid (for example, Ethylenediamine tetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexane diamine tetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo -
N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and their salts), 4,4'-diamino-2 Fluorescent brighteners such as 2,2'-disulfostyrenebenne compounds, alkylsulfonic acids, arylsulfonic acids, aliphatic carboxylic acids,
Various surfactants such as aromatic carboxylic acids may be added.

However, it is preferable that benzyl alcohol is not substantially contained in terms of pollution, liquid preparation and prevention of color contamination. Here, "substantially" means 2 ml or less (more preferably not containing at all) per liter of color developing solution. When the reversal process is performed, color development is usually performed after black and white development. The black-and-white developer includes dihydroxybenzenes such as hydroquinone, 1-phenyl-3
Known black-and-white developing agents such as 3-pyrazolidones such as -pyrazolidone or aminophenols such as N-methyl-p-aminophenol can be used alone or in combination.

The pH of the color developing solution and the black and white developing solution
Is generally 9 to 12. The replenishing amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per square meter of the photographic material, and can be reduced to 500 ml or less by reducing the bromide ion concentration in the replenishing solution. You can also. In particular,
When a so-called high silver chloride light-sensitive material is used, by lowering bromine ions in the color developing solution and relatively increasing chloride ions, photographic properties and processing properties are excellent, and fluctuations in photographic properties can be suppressed. This is particularly preferred. In such a case, the replenishing amount can be reduced to about 20 ml per square meter of the light-sensitive material, in which overflow in the color developing bath is substantially eliminated. When the replenishment rate is reduced, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the processing tank with the air. Further, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developer.

The processing temperature of the color developing solution of the present invention is from 20 to
At 50 ° C, preferably 30 to 45 ° C. Processing time is
The processing time is 20 seconds to 5 minutes, preferably 30 seconds to 3 minutes, but the processing time can be further shortened by using a high temperature and high pH and using a high concentration of the color developing agent.

The photographic emulsion layer after color development is usually subjected to bleaching. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. In order to further speed up the processing, a processing method of performing bleach-fixing after bleaching may be used. Further, processing in two successive bleach-fixing baths, fixing before bleach-fixing, or bleaching after bleach-fixing can be arbitrarily performed according to the purpose. Examples of the bleaching agent include compounds of polyvalent metals such as iron (III), cobalt (III), chromium (IV), and copper (II);
Peracids, quinones, nitro compounds and the like are used. Typical bleaching agents are ferricyanide; dichromate; organic complex salts of iron (III) or cobalt (III), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid,
Aminopolycarboxylic acids such as 1,3-diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, or complex salts such as citric acid, tartaric acid, and malic acid; persulfates;
Bromate; permanganate; nitrobenzenes and the like can be used. Of these, iron (III) complex salts of aminopolycarboxylic acid such as iron (III) complex salt of ethylenediaminetetraacetate are preferable in terms of persulfate from the viewpoint of rapid treatment and prevention of environmental pollution. Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in a bleaching solution and a bleach-fixing solution. In particular, the bleaching solution for negative photosensitive materials for photography includes 1,
Iron (III) complex salt of 3-diaminopropanetetraacetate is preferred from the viewpoint of bleaching ability. These aminopolycarboxylic acid iron (II
I) The pH of the bleaching solution or the bleach-fixing solution using a complex salt is usually 5.5 to 8, but the processing can be carried out at a lower pH in order to speed up the processing.

In the bleaching solution, the bleach-fixing solution and the prebath thereof, a bleaching accelerator can be used if necessary.
Specific examples of useful bleach accelerators are described in the following specification. U.S. Pat. No. 3,893,858, West German Patent Nos. 1,290,812, 2,059,988, JP-A-53-32736, JP-A-53-57831, and JP-A-53-57831.
No. 37418, No. 53-72623, No. 53-95
No. 630, No. 53-95731, No. 53-10423
No. 2, No. 53-124424, No. 53-141623
No. 53-28426, RD No. 17129 (1
A compound having a mercapto group or a disulfide group described in, for example, Japanese Patent Application Laid-Open No. Sho 50-140129; Japanese Patent Publication No. 45-8506.
JP-A-52-20832 and JP-A-53-32735.
Thiourea derivatives described in U.S. Patent No. 3,706,561; West German Patent No. 1,127,715;
Iodide salts described in US Pat. No. 16,235; West German Patent No. 96
Polyoxyethylene compounds described in JP-A-6-410 and JP-A-2,748,430; polyamine compounds described in JP-B-45-8836;
Nos. 49-59644, 53-94927, 54
No. 35727, No. 55-26506, No. 58-16
Compounds described in No. 3940; bromide ions and the like can be used. Among them, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large accelerating effect, and in particular, US Pat. No. 3,893,858 and West German Patent 1,290,
No. 812 and compounds described in JP-A-53-95630 are preferred. Further, the compounds described in U.S. Pat. No. 4,552,834 are also preferred. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color photographic material for photography.

Known additives such as rehalogenating agents such as ammonium bromide and ammonium chloride, pH buffering agents such as ammonium nitrate, and metal corrosion inhibitors such as ammonium sulfate can be added to the bleach-fixing solution of the present invention. . Known fixing agents may be used in the fixing bath of the present invention in addition to the compound of the present invention. For example, examples of the fixing agent include thiosulfate, thiocyanate, thioether-based compounds, thioureas, and a large amount of iodide.The use of thiosulfate is generally used. It is preferable from the viewpoint of solubility and fixing speed, and may be used in combination with another fixing agent. As a preservative of the bleach-fix solution, a sulfite, a bisulfite, a carbonyl bisulfite adduct, and a sulfinic acid compound are preferable. In order to improve the stability of the fixing solution, amino fixing agents such as aminopolycarboxylic acids and organic phosphonic acid chelating agents (preferably 1-hydroxyethylidene-1,1-diphosphonic acid and N, N, N ',
(N'-ethylenediaminetetraphosphonic acid).

The fixing solution may further contain various fluorescent whitening agents, antifoaming agents, surfactants, polyvinylpyrrolidone, methanol and the like. It is preferable that the stirring of each processing solution in the desilvering step is strengthened as much as possible from the viewpoint of shortening the desilvering processing time. Examples of the stirring means include the methods described in JP-A-62-183460 and JP-A-62-183461. In the case of the means for impinging the jet, the time until the collision is such that the photosensitive material is treated with the processing liquid. Preferably, it is performed within 15 seconds after the introduction.

In the present invention, the crossover time from the color developing solution to the bleaching solution (the air time from the time when the photosensitive material leaves the color developing solution to the time when entering the bleaching solution) is improved in terms of bleaching fog and adhesion of dirt on the surface of the photosensitive material. The time is preferably within 10 seconds. Further, the crossover time from the bleaching solution of the invention to the processing solution having fixing ability is preferably within 10 seconds from the viewpoint of improving the poor recoloring of the cyan dye. Here, the replenishment amount of the fixing solution is preferably 800 ml / m ² or less in the case of a color light-sensitive material for photography (for example, a coated silver amount of 4 to 12 g / m ² ). It is preferably 50 ml / m ² or less.

The silver halide color photographic light-sensitive material used in the present invention generally undergoes a washing and / or stabilizing step after desilvering. The amount of rinsing water in the rinsing process depends on the characteristics of the photosensitive material (for example, depending on the material used such as a coupler), the use, the rinsing water temperature, the number of rinsing tanks (number of stages), countercurrent,
It can be set in a wide range according to a replenishment method such as a forward flow and other various conditions. Of these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent method is described in the Journal of the Society of Moti
on Picture and Television Engineers, vol. 64, p.
248-253 (May 1955)
You can ask. According to the multi-stage countercurrent method described in the literature, the amount of washing water can be significantly reduced, but bacteria increase due to an increase in the residence time of water in the tank,
There is a problem that the generated suspended matter adheres to the photosensitive material. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, the method of reducing Ca ions and Mg ions described in JP-A-62-288838 can be used very effectively. Also, Japanese Patent Application Laid-Open No. 57-85
No. 42, isothiazolone compounds, thiabendazoles, chlorinated bactericides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc. Sterilization, sterilization,
Fungicides described in "Antifungal Technology", "Encyclopedia of Antifungal Agents" edited by the Japan Society of Antifungals and Fungi.

The pH of the washing water in the processing of the light-sensitive material of the present invention is from 4 to 9, preferably from 5 to 8. The washing temperature and washing time can also be variously set depending on the characteristics of the photosensitive material, the use, etc., but are generally at 15 to 45 ° C. for 20 seconds to 10 minutes,
Preferably, a range of 30 seconds to 5 minutes at 25 to 40 ° C is selected. Further, the light-sensitive material of the present invention can be processed directly with a stabilizing solution instead of the above-mentioned water washing. In such a stabilizing process, JP-A-57-8543 and JP-A-58-8543 are used.
All known methods described in JP-A-14834 and JP-A-60-220345 can be used.

In some cases, a stabilization treatment may be performed after the water washing treatment. For example, for example, formalin, hexamethylenetetramine, hexahydrotriazine, N-hydrogenazine, etc., which are used as a final bath of a color light-sensitive material for photography. A stabilizing bath containing a dye stabilizer represented by a methylol compound can be exemplified. If necessary, a metal compound such as an ammonium compound, Bi, or Al, a fluorescent brightener, various chelating agents, a film pH regulator, a hardening agent, a bactericide, an antifungal agent, an alkanolamine, or a surfactant may be used in this stabilizing bath. An agent (preferably a silicon-based agent) can also be added. The water used in the washing step or the stabilization step includes tap water, water that has been deionized to a Ca ion and Mg ion concentration of 5 mg / liter or less with an ion exchange resin, halogen, and water that has been sterilized with a UV germicidal lamp or the like. It is preferred to use

The replenishment amount of the above-mentioned washing and / or stabilizing solution may be 1 to 50 of the amount brought in from the previous bath per unit area of the light-sensitive material.
Times, preferably 2 to 30 times, more preferably 2 to 15 times. The overflow solution accompanying this replenishment can be reused in the desilvering step and other steps. The silver halide color light-sensitive material to be processed in the present invention may contain a color developing agent for the purpose of simplifying and speeding up the processing. In order to incorporate the color developing agent, it is preferable to use various precursors of a color developing agent. For example, indoaniline compounds described in U.S. Pat. No. 3,342,597, and 3,342,599
No. 14,850 and 15,159, Schiff base compounds, aldol compounds described in 13,924, metal salt complexes described in US Pat. No. 3,719,492, And urethane compounds described in JP-A-135628. The silver halide color light-sensitive material processed in the present invention may contain various 1-phenyl-3-pyrazolidones, if necessary, for the purpose of accelerating color development. A typical compound is disclosed in
Nos. 64339, 57-1444547 and 58-
No. 115438 and the like.

The various processing solutions used in the present invention are in the range of 10 ° C. to 50
Used at ° C. Usually, a temperature of 33 ° C. to 38 ° C. is standard, but a higher temperature promotes the processing and shortens the processing time, and a lower temperature achieves an improvement in the image quality and an improvement in the stability of the processing solution. be able to.

As one example of a silver halide color light-sensitive material, there is one using direct positive silver halide. The processing using this photosensitive material will be described below. A surface developer having a pH of 11.5 or less containing an aromatic primary amine color developer after imagewise exposure of a silver halide color photographic light-sensitive material, or after or while performing fog treatment with light or a nucleating agent. It is also preferable to form a positive color image directly by color development, bleaching and fixing. The pH of the developer is more preferably in the range of 11.0 to 10.0. The fogging treatment in the present invention includes a method of applying a second exposure to the entire surface of a photosensitive layer called a so-called "light fogging method" and a method of developing in the presence of a nucleating agent called a "chemical fogging method". Either one may be used. Development processing may be performed in the presence of a nucleating agent and fog light. Further, the photosensitive material containing the nucleating agent may be exposed to fog.

Regarding the light fogging method, see the aforementioned Japanese Patent Application No.
No. 253716, page 47, line 4 to page 49, line 5; nucleating agents that can be used in the present invention are described in page 49, line 6 to page 67, line 2; In particular, use of the compounds represented by the general formulas [N-1] and [N-2] is preferred. Specific examples of these are described in the fifth specification of the same specification.
[NI-1] to [NI-10] described on pages 6 to 58
And [N-II-1] on pages 63 to 66 of the same specification.
The use of [N-II-12] is preferred. With respect to the nucleation promoter that can be used in the present invention, the same specification, page 68, line 11 to 71
It is described on page 3, line 3, and as this specific example, the use of (A-1) to (A-13) described on pages 69 to 70 is particularly preferable.

Next, a silver halide black-and-white photographic light-sensitive material and processing using the same will be described in detail. The halogen composition of the silver halide emulsion used is not particularly limited, and may be any composition such as silver chloride, silver chlorobromide, silver iodobromide, silver bromide, silver iodobromochloride, etc. The silver halide content is preferably at most 10 mol%, particularly preferably at most 5 mol%. When used for forming a high-contrast negative image, the silver halide used has an average grain size of fine grains (for example, 0.7 grains).
μ) or less, more preferably 0.5 μ or less. The particle size distribution is basically not limited, but is preferably monodispersed. The monodispersion as used herein means that at least 95% of the weight or the number of particles is ±± of the average particle size.
It means that it is composed of a particle group having a size within 40%. Silver halide grains in photographic emulsions are regular, such as cubic, octahedral, rhombodecahedral, and tetradecahedral.
It may be one having an irregular crystal, one having an irregular crystal such as a sphere or a plate, or one having a complex of these crystal forms.

Regarding the other points of the photographic emulsion, the above-mentioned photographic emulsion can be basically used. In the present invention, the silver halide emulsion layer preferably contains two types of monodisperse emulsions having different average grain sizes as disclosed in Japanese Patent Application Nos. 60-64199 and 60-232086. ) It is preferable in terms of increase, and the small-sized monodispersed particles are preferably chemically sensitized, and the method of chemical sensitization is most preferably sulfur sensitization. The large-size monodisperse emulsion may not be chemically sensitized, but may be chemically sensitized. Generally, large-sized monodispersed particles are not subjected to chemical sensitization because black spots are easily generated. However, when chemically sensitized, it is particularly preferable to apply the light as shallow as not to generate black spots. Here, "shallow application" refers to shortening the time for chemical sensitization, lowering the temperature, or reducing the amount of chemical sensitizer added as compared with the chemical sensitization of small-sized grains. The difference in sensitivity between the large-sized monodispersed emulsion and the small-sized monodispersed emulsion is not particularly limited.
0, more preferably 0.2 to 0.7, and the higher the large-sized monodispersed emulsion, the more preferable. The average grain size of the small-sized monodispersed grains is 90% or less, preferably 80% or less, of the average size of the large-sized silver halide monodispersed grains.

The photographic light-sensitive material used in the present invention may contain a known nucleating agent in a photographic emulsion layer or another hydrophilic colloid layer to form a super-high contrast image. As the nucleating agent used in the present invention, for example, RESEARCH DISCL
OSURE Item 23516 (November 1983, p.
346) and the references cited therein. Examples of development accelerators suitable for use in the present invention or accelerators for nucleation and infectious development include JP-A-53-77616.
No. 54-37732, No. 53-137133,
In addition to the compounds disclosed in JP-A-60-140340 and JP-A-60-14959, various compounds containing an N or S atom are effective.

The direct-positive light-sensitive material used in the present invention may contain a desensitizer in the photographic emulsion layer and other hydrophilic colloid layers. The organic desensitizer is defined by its polarographic half-wave potential, that is, the oxidation-reduction potential determined by polarography, and the sum of the polaro anodic potential and the cathodic potential becomes positive. As an organic desensitizer, Japanese Patent Application No. 61-
Those represented by the general formulas (III) to (V) described on pages 55 to 72 of 280998 are preferably used.

In the method of the present invention, a developing solution for developing a silver halide black-and-white light-sensitive material contains a commonly used additive (eg, a developing agent, an alkali agent, a pH buffer, a preservative, a chelating agent). It can be contained. For the treatment of the present invention, any of the known methods can be used, and a known treatment solution can be used. or,
The processing temperature is usually chosen between 18 ° C and 50 ° C,
The temperature may be lower than 18 ° C or higher than 50 ° C. Black-and-white developers include dihydroxybenzenes (for example, hydroquinone), 1-phenyl-3-pyrazolidones, and aminophenols (for example, N-methyl-p-).
Known developing agents such as aminophenol) can be used alone or in combination.

The dihydroxybenzene-based developing agent is preferably used usually in an amount of 0.05 mol / l to 0.8 mol / l. Also, dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p-amino-
When the combination with phenols is used, the former is 0.0
5 mol / l to 0.5 mol / l, the latter being 0.1 mol / l.
It is preferably used in an amount of not more than 06 mol / liter. Examples of the sulfite preservative used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, sodium bisulfite, potassium metabisulfite, and sodium formaldehyde bisulfite. Sulfite is used in a black-and-white developer, particularly in a graphic arts developer, in an amount of 0.3 mol / l or more. However, if an excessively large amount is added, it precipitates in the developer and causes liquid contamination, so the upper limit is 1.2 mol / l. It is preferred that

The alkaline agent used in the developer of the present invention may be a pH such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium tertiary phosphate, potassium tertiary phosphate, sodium silicate or potassium silicate. Contains regulators and buffers. As additives used in addition to the above components, boric acid, compounds such as borax, sodium bromide,
Development inhibitors such as potassium bromide and potassium iodide: ethylene glycol, diethylene glycol, toluene glycol, dimethylformamide, methyl cellosolve,
Organic solvents such as hexylene glycol, ethanol and methanol: mercapto compounds such as 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole-5-sulfonic acid sodium salt, indazole compounds such as 5-nitroindazole, 5 An antifoggant such as a benztriazole-based compound such as methylbenztriazole or a black pepper inhibitor; and, if necessary, a color tone agent, a surfactant, an antifoaming agent, a water softener, Hardeners and the like may be included. Compounds described in JP-A-56-24347 are used as silver stain inhibitors, and JP-A-62-21265 are used as development unevenness preventing agents.
Compounds described in No. 1 as dissolution aids
The compounds described in No. 9743 can be used.

In the developer used in the present invention, boric acid described in Japanese Patent Application No. 61-28708, saccharides (for example, saccharose) and oximes (for example, Oximes), phenols (for example, 5-sulfosalicylic acid), and tertiary phosphates (for example, sodium salts and potassium salts). The fixing solution is an aqueous solution containing a hardener (for example, a water-soluble aluminum compound), acetic acid, and a dibasic acid (for example, tartaric acid, citric acid, or a salt thereof), if necessary, in addition to the fixing agent. 8 or more, more preferably 4.
0-7.5. Known fixing agents may be used in combination with the compound of the present invention in the fixing bath of the present invention. For example, the fixing agent is sodium thiosulfate, ammonium thiosulfate, or the like, and ammonium thiosulfate is particularly preferable from the viewpoint of fixing speed. The amount of the fixing agent to be used can be appropriately changed and is generally about 0.1 to about 0.5 mol / l. The water-soluble aluminum salt mainly used as a hardening agent in the fixing solution is a compound generally known as a hardening agent for an acidic hardening fixing solution, and examples thereof include aluminum chloride, aluminum sulfate and potassium alum. As the above-mentioned dibasic acid, tartaric acid or a derivative thereof, citric acid or a derivative thereof can be used alone or in combination of two or more. It is effective that these compounds contain 0.005 mol or more per liter of the fixing solution, and particularly 0.01 to 0.03 mol / l is particularly effective. Specifically, there are tartaric acid, potassium tartrate, sodium tartrate, potassium sodium tartrate, ammonium tartrate, potassium ammonium tartrate, and the like.

The fixing solution may further contain a preservative (for example, sulfite or bisulfite), a pH buffer (for example, acetic acid or boric acid), a pH adjuster (for example, ammonia or sulfuric acid), or an image preserving agent, if desired. Agents (eg, potassium iodide) and chelating agents. Here, the pH buffer is used in an amount of 10 to 40 g / liter, more preferably about 18 to 25 g / liter, because the pH of the developer is high. The fixing temperature and time are the same as in the case of the development.
0 seconds to 1 minute is preferred. Here, the replenishment rate of the fixing solution is preferably 300 ml / m ² or less.

As the washing water, those described above can be used. Further, a stabilizer may be used in place of the washing water. The roller transport type automatic developing machine is described in U.S. Pat. Nos. 3,025,779 and 3,545,971 and the like, and is simply referred to as a roller transport type processor in this specification. The roller transport type processor has four steps of development, fixing, washing and drying, and the method of the present invention does not exclude other steps (for example, a stop step), but most preferably follows these four steps. . Here, in the rinsing step, water can be saved by using two to three stages of countercurrent rinsing.

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EXAMPLES The present invention will be described in detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto.

Example 1 On a paper support laminated on both sides with polyethylene, a multilayer color photographic paper having the following layer constitution was produced. The coating solution was prepared as follows. Preparation of First Layer Coating Solution 19.1 g of yellow coupler (ExY), 4.4 g of color image stabilizer (Cpd-1) and color image stabilizer (Cpd-)
7) 27.2 cc of ethyl acetate and solvent (So
lv-1) 8.2 g was added and dissolved, and the solution was added to 10% sodium dodecylbenzenesulfonate containing 8 cc of 10%
It was emulsified and dispersed in 185 cc of an aqueous gelatin solution. On the other hand, a silver chlorobromide emulsion (cubic, 3: 7 mixture (molar ratio) of an average grain size of 0.88 μm and an average grain size of 0.70 μm. The variation coefficient of the grain size distribution was 0.08 and 0.10. The emulsion contains 0.2 mol% of silver bromide locally on the grain surface), and the following blue-sensitive sensitizing dye is added in an amount of 2.0 × 10 ⁻⁴ mol per mol of silver per mol of silver emulsion. In addition, small emulsions were prepared by adding 2.5 × 10 ^-4 mol of each and then sensitizing with sulfur. The above-mentioned emulsified dispersion and this emulsion were mixed and dissolved to prepare a first coating solution having the composition shown below.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. As a gelatin hardener for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. The following were used as spectral sensitizing dyes for each layer. Blue-sensitive emulsion layer

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Green-sensitive emulsion layer

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Red-sensitive emulsion layer

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The following compounds were added to the red-sensitive emulsion layer in an amount of 2.6 × 10 ^-4 mol per mol of silver halide.

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The blue-sensitive emulsion layer, the green-sensitive emulsion layer, and the red-sensitive emulsion layer were treated with 1- (5-methylureidophenyl).
8.5 × 10 ^-5 mol, 7.7 × 10 ^-4 mol and 2.5 × 10 ^-4 mol of ^-5 -mercaptotetrazole were added per mol of silver halide, respectively. Further, 4-hydroxy-6-methyl-to-blue-sensitive emulsion layer and green-sensitive emulsion layer
1,3,3a, 7-Tetrazaindene were added in an amount of 1 × 10 ^-4 mol and 2 × 10 ^-4 mol, respectively, per mol of silver halide. The following dyes were added to the emulsion layer to prevent irradiation.

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(Layer Structure) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver. Support Polyethylene laminated paper [The first layer of polyethylene contains white pigment (TiO ₂ ) and bluish dye (ultra blue)]

First layer (blue-sensitive layer) The silver chlorobromide emulsion 0.30 gelatin 1.86 yellow coupler (ExY) 0.82 color image stabilizer (Cpd-1) 0.19 solvent (Solv-1) 0.35 Color image stabilizer (Cpd-7) 0.06 Second layer (color mixture preventing layer) Gelatin 0.99 Color mixture inhibitor (Cpd-5) 0.08 Solvent (Solv-1) 0.16 Solvent (Solv) -4) 0.08

Third Layer (Green Sensitive Layer) Silver chlorobromide emulsion (cubic, 1: 3 mixture of 0.55 μm and 0.39 μm particles (Ag mole ratio), particle size distribution The coefficient of variation was 0.10 and 0.08, and each emulsion contained 0.8 mol% of AgBr locally on the surface of the grains.) 0.12 Gelatin 1.24 Magenta coupler (ExM) 0.20 Color image stabilizer ( Cpd-2) 0.03 Color image stabilizer (Cpd-3) 0.15 Color image stabilizer (Cpd-4) 0.02 Color image stabilizer (Cpd-9) 0.02 Solvent (Solv-2) 0 .40 fourth layer (ultraviolet ray absorbing layer) gelatin 1.58 ultraviolet ray absorbent (UV-1) 0.47 color mixture inhibitor (Cpd-5) 0.05 solvent (Solv-5) 0.24

Fifth Layer (Red Sensitive Layer) Silver chlorobromide emulsion (cubic, 1: 4 mixture of 0.58 μm and 0.45 μm) (Ag molar ratio), The coefficient of variation was 0.09 and 0.11, and each emulsion contained 0.6 mol% of AgBr locally on the grain surface.) 0.23 Gelatin 1.34 Cyan coupler (ExC) 0.32 Color image stabilizer ( Cpd-6) 0.17 Color image stabilizer (Cpd-7) 0.40 Color image stabilizer (Cpd-8) 0.04 Solvent (Solv-6) 0.15 Sixth layer (ultraviolet absorbing layer) Gelatin 0 .53 UV absorber (UV-1) 0.16 Color mixture inhibitor (Cpd-5) 0.02 Solvent (Solv-5) 0.08 Seventh layer (protective layer) Gelatin 1.33 Acrylic modified polyvinyl alcohol Polymer (degree of modification 17%) 0.17 Listed for the compounds used in the above dynamic paraffin 0.03.

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After the sample prepared as described above was cut, the sample was exposed to black and white, and was continuously processed using a paper processing machine until the replenishment amount of the bleach-fixing solution became twice the tank capacity in the following processing steps. (Running test).

Processing step Temperature Time Replenishment amount ^* Tank capacity (liter) Color development 39 ° C 45 seconds 70 ml 20 Bleaching and fixing 35 ° C 25 seconds 60 ml ^** 20 or 40 ml ^** Rinse 35 ° C 20 seconds-10 rinse 35 ° C 20 sec - 10 rinse 35 ° C. 20 seconds 360 ml 10 drying 80 ° C. 60 seconds in addition to the (third tank was countercurrent system to rinse →) * photosensitive material 1 m ² per replenishment amount ** above 60 ml, light-sensitive than the rinse material it does this flow of 1m ² per 120ml

Color developer Tank solution Replenisher Water 700 ml 700 ml Diethylenetriaminepentaacetic acid 0.4 g 0.4 g N, N, N-trimethylenephosphonic acid 4.0 g 4.0 g 1-hydroxyethylidene-1,1-diphos 0.4 g 0.4 g fonic acid Triethanolamine 12.0 g 12.0 g Potassium chloride 6.5 g-Potassium bromide 0.03 g-Potassium carbonate 27.0 g 27.0 g Fluorescent whitening agent (WHITEX 4B manufactured by Sumitomo Chemical) 1.0 g 3.0 g Sodium sulfite 0.1 g 0.1 g N, N-bis (Sulfoethyl) hydroxyl 10.0 g 13.0 g Amine N-ethyl-N- (β-methanesulfonami 5.0 g 11.5 g ethyl) -3-methyl-4-aminoaniline sulfate Water was added to 1000 ml 1000 ml pH (25 ° C) 10.10 11.10

Bleach-fixing solution Tank solution Replenisher Replenisher Water 500 ml 100 ml 100 ml Fixing agent (see Table 1) 0.5 mol 1.25 mol 1.25 mol Ammonium sulfite 40 g 100 g 100 g (Use only when the fixing agent is ammonium thiosulfate) Ferrous ammonium 0.15 mol 0.37 mol 0.37 mol Aluminum dihydrate Chelating agent (same as bleach) 0.02 mol 0.04 mol 0.04 mol Ammonium bromide 40 g 75 g 150 g Nitric acid (67%) 30 g 65 g 100 g Add water 1000 ml 1000 ml 1000 ml pH (25 ° C) (adjusted with acetic acid and ammonia) 5.8 5.6 5.4 Rinse solution (same as tank solution and replenisher) Ion-exchanged water (3 ppm or less for calcium and magnesium each)

[Evaluation of Desilvering Performance] With respect to the black-and-white exposed film before the end of the running process, the amount of residual silver in the unexposed area was measured using a fluorescent X-ray analyzer. [Evaluation of Liquid Stability] Further, the presence or absence of a precipitate in the bleach-fix bath and the rinsing bath after the running treatment was visually examined. The evaluation was performed based on the following criteria. ：: no precipitation by visual inspection △: small amount of precipitation ×: large amount of precipitation

Table 1 shows the results.

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[Table 1]

From Table 1, it can be seen that when the compound of the present invention was used, no precipitation occurred during running processing, the liquid stability was good, and the fixing performance was better than that of thiosulfate. Obtained. This effect is particularly remarkable when the replenishment rate is reduced.

Example 2 Compound-2 of Example 1 was replaced with Compounds-3, 5, 10, 16,
17, 25, 33, 34, 36, 37, 38 or 44
And the same tests as in Example 1 were performed. As a result, good results were obtained in which the fixing ability was high as in Example 1, and no precipitation occurred during the running process. It was also found that this effect was particularly remarkable when the replenishment was reduced.

Example 3 In Example 1, the bleaching agent in the bleach-fix solution was replaced with ammonium ferric ethylenediaminetetraacetate dihydrate in an equimolar manner with ammonium ferric 1,3-propylenediaminetetraacetate monohydrate. The same test as in Example 1 was performed except for the above. Table 2 shows the results.

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[Table 2]

From Table 2, it can be seen that when the compound of the present invention was used, no precipitate was formed during the running process, and the solution stability was much better than that of thiosulfate. Excellent good results were obtained.
This effect was particularly remarkable when the replenishment was reduced.

Example 4 On an undercoated cellulose triacetate film support,
Sample 101, which is a multilayer color photographic material composed of each layer having the following composition, was prepared. The amount of silver coverage (Composition of photosensitive layer) The silver halide and colloidal silver, expressed in units of g / m ^2, also a coupler, the amount for the additives and gelatin, expressed in units of g / m ^2, The sensitizing dyes are shown in terms of moles per mole of silver halide in the same layer.

First layer: Antihalation layer Black colloidal silver Silver coating amount 0.20 Gelatin 2.20 UV-1 0.11 UV-2 0.20 Cpd-1 4.0 × 10 ^-2 Cpd-2 9 × 10 ⁻² Solv-1 0.30 Solv-2 1.2 × 10 ⁻² Second layer: intermediate layer Fine grain silver iodobromide (AgI 1.0 mol%, equivalent sphere diameter 0.07 μm) Silver coating amount 0.15 Gelatin 1.00 ExC-4 6.0 × 10 ^-2 Cpd-3 2.0 × 10 ^-2

Third Layer: First Red-Sensitive Emulsion Layer Silver iodobromide emulsion (AgI 5.0 mol%, surface high AgI type, equivalent sphere diameter 0.9 μm, coefficient of variation of equivalent sphere diameter 21%, tabular grains, diameter / Thickness ratio 7.5) Silver coating amount 0.42 Silver iodobromide emulsion (AgI 4.0 mol%, internal high AgI type, equivalent spherical diameter 0.4 μm, coefficient of variation of equivalent spherical diameter 18%, tetradecahedral grains) 0.40 Gelatin 1.90 ExS-1 4.5 × 10 ^-4 mol ExS-2 1.5 × 10 ^-4 mol ExS-3 4.0 × 10 ^-5 mol ExC-1 0.65 ExC-3 1 0.0 × 10 ^-2 ExC-4 2.3 × 10 ^-2 Solv-1 0.32

Fourth Layer: Second Red-Sensitive Emulsion Layer Silver iodobromide emulsion (AgI 8.5 mol%, internal high AgI type, equivalent spherical diameter 1.0 μm, coefficient of variation of equivalent spherical diameter 25%, plate-like grains, diameter / Thickness ratio 3.0) Silver coating amount 0.85 Gelatin 0.91 ExS-1 3.0 × 10 ^-4 mol ExS-2 1.0 × 10 ^-4 mol ExS-3 3.0 × 10 ^-5 mol ExC-1 0.13 ExC-2 6.2 × 10 ^-2 ExC-4 4.0 × 10 ^-2 Solv-1 0.10 Fifth layer: Third red-sensitive emulsion layer Silver iodobromide emulsion (AgI 11.3 mol%, Internal high AgI type, equivalent sphere diameter 1.4 μm, coefficient of variation of equivalent sphere diameter 28%, plate-like particles, diameter / thickness ratio 6.0) Silver coating amount 1.50 Gelatin 1.20 ExS-1 2.0 × 10 ^-4 Mol ExS-2 6.0 × 10 ⁻⁵ mol ExS-3 2.0 × 10 ⁻⁵ mol ExC-2 8.5 × 10 ⁻² ExC-5 7.3 × 10 ^-2 Solv-1 0.12 Solv-2 0.12

Sixth layer: Intermediate layer Gelatin 1.00 Cpd-4 8.0 × 10 ^-2 Solv-1 8.0 × 10 ^-2 Seventh layer: First green-sensitive emulsion layer Silver iodobromide emulsion (AgI 5.0 mol%, surface high AgI type, equivalent sphere diameter 0.9 μm, coefficient of variation of equivalent sphere diameter 21%, tabular grains, diameter / thickness ratio 7.0) Silver coating amount 0.28 Silver iodobromide emulsion (AgI 4.0 mol%) , Internal high AgI type, equivalent spherical diameter 0.4 μm, coefficient of variation of equivalent spherical diameter 18%, tetradecahedral particles) Silver coating amount 0.16 gelatin 1.20 ExS-4 5.0 × 10 ⁻⁴ mol ExS− 5 2.0 × 10 ⁻⁴ mol ExS-6 1.0 × 10 ⁻⁴ mol ExM-1 0.50 ExM-2 0.10 ExM-5 3.5 × 10 ⁻² Solv-1 0.20 Solv− 3 3.0 × 10 ^-2

Eighth Layer: Second Green-Sensitive Emulsion Layer Silver iodobromide emulsion (AgI 8.5 mol%, internal high AgI type, sphere equivalent diameter 1.0 μm, sphere equivalent diameter variation coefficient 25%, plate-like grains, diameter / Thickness ratio 3.0) Silver coating amount 0.57 Gelatin 0.45 ExS-4 3.5 × 10 ^-4 mol ExS-5 1.4 × 10 ^-4 mol ExS-6 7.0 × 10 ^-5 mol ExM-1 0.12 ExM-2 7.1 × 10 ⁻³ ExM-3 3.5 × 10 ⁻² Solv-1 0.15 Solv-3 1.0 × 10 ⁻² Ninth layer: Intermediate layer Gelatin 0.50 Solv -1 2.0 × 10 ^-2

Tenth Layer: Third Green-Sensitive Emulsion Layer Silver iodobromide emulsion (AgI 11.3 mol%, internal high AgI type, equivalent sphere diameter 1.4 μm, coefficient of variation of equivalent sphere diameter 28%, tabular grains, diameter / Thickness ratio 6.0) Silver coating amount 1.30 Gelatin 1.20 ExS-4 2.0 × 10 ⁻⁴ mol ExS-5 8.0 × 10 ⁻⁵ mol ExS-6 8.0 × 10 ⁻⁵ mol ExM-4 4.5 × 10 ^-2 ExM-6 1.0 × 10 ^-2 ExC-2 4.5 × 10 ^-3 Cpd-5 1.0 × 10 ^-2 Solv-1 0.25 Eleventh layer: Yellow filter layer Gelatin 0.50 Cpd-6 5.2 × 10 ^-2 Solv-1 0.12 12th layer: Intermediate layer Gelatin 0.45 Cpd-3 0.10

Thirteenth layer: First blue-sensitive emulsion layer Silver iodobromide emulsion (AgI 2 mol%, uniform AgI type, equivalent sphere diameter 0.55 μm, coefficient of variation of equivalent sphere diameter 25%, tabular grains, diameter / thickness Ratio 7.0) Silver coating amount 0.20 Gelatin 1.00 ExS-7 3.0 × 10 ⁻⁴ mol ExY-1 0.60 ExY-2 2.3 × 10 ⁻² Solv-1 0.15 14th layer: Second blue-sensitive emulsion layer Silver iodobromide emulsion (AgI 19.0 mol%, internal high AgI type, equivalent sphere diameter 1.0 μm, variation coefficient of equivalent sphere diameter 16%, octahedral grains) Silver coating amount 0.19 gelatin 0. 35 ExS-7 2.0 × 10 ⁻⁴ mol ExY-1 0.22 Solv-1 7.0 × 10 ⁻²

Fifteenth layer: Intermediate layer Fine grain silver iodobromide (AgI 2 mol%, uniform AgI type, equivalent sphere diameter 0.13 μm) Silver coating amount 0.20 Gelatin 0.36 16th layer: Third blue-sensitive emulsion layer Silver iodobromide emulsion (AgI 14.0 mol%, internal high AgI type, equivalent sphere diameter 1.7 μm, coefficient of variation of equivalent sphere diameter 28%, plate-like grains, diameter / thickness ratio 5.0) Silver coating amount 1.55 Gelatin 1. 00 ExS-8 1.5 × 10 ⁻⁴ mol ExY-1 0.21 Solv-1 7.0 × 10 ⁻²

17th layer: 1st protective layer Gelatin 1.80 UV-1 0.13 UV-2 0.21 Solv-1 1.0 × 10 ^-2 Solv-2 1.0 × 10 ^-2 18th layer : Second protective layer Fine particle silver chloride (sphere equivalent diameter 0.07 μm) Silver coating amount 0.36 Gelatin 0.70 B-1 (1.5 μm diameter) 2.0 × 10 ^-2 B-2 (1.5 μm diameter) 15 B-3 3.0 × 10 ^-2 W-1 2.0 × 10 ^-2 H-1 0.35 Cpd-7 1.00

The samples prepared in this manner include, in addition to the above,
1,2-Benzisothiazolin-3-one (average 200 ppm based on gelatin), n-butyl-p-hydroxybenzoate (about 1,000 ppm), and 2-phenoxyethanol (about 10,000 ppm) were added. . Further, B-4, B-5, W-2, W-3, F-1, F-
2, F-3, F-4, F-5, F-6, F-7, F-
8, F-9, F-10, F-11, F-12, F-13
And iron salts, lead salts, gold salts, platinum salts, iridium salts, and rhodium salts.

The compounds used above are listed below.

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After the sample prepared as described above was cut, exposed to black and white, and subjected to continuous processing using an automatic processing machine until the replenishment amount of the bleach-fixing solution became twice the tank capacity in the following processing step. (Running test).

Processing process Temperature Time Replenishment amount ^* Tank capacity (liter) Color development 38.0 ° C 3 minutes 05 seconds 600ml 17 Bleaching and fixing 38.0 ° C 50 seconds -5 Bleaching and fixing 38.0 ° C 1 minute 400ml 5 or 360ml Washing 38.0 ° C 30 sec 900 ml 3 stabilization 38.0 ° C. 20 sec - 3 stabilization 38.0 ° C. 20 sec 560 ml 3 drying 80 ° C. 60 seconds * photosensitive material 1 m ² per replenishment rate bleach-fixing solution, stabilizing solution is countercurrent system from to. The amount of the developer brought into the bleach-fixing step and the amount of the bleach-fix solution brought into the washing step were 65 ml and 50 ml, respectively, per m ² of the light-sensitive material. The crossover time is 6 seconds in each case, and this time is included in the processing time of the previous process. Each replenisher was replenished with the same liquid as the respective tank liquid. The composition of the treatment liquid is shown below.

Color developing solution Start solution Replenisher Diethylenetriaminepentaacetic acid 2.0 g 2.0 g 1-hydroxyethylidene-1,1-diphos 3.3 g 3.3 g Sodium sulfonate 3.9 g 5.1 g Potassium carbonate 37.5 g 39.0 g Potassium bromide 1.4 g 0.4 g Potassium iodide 1.3 mg-Hydroxylamine sulfate 2.4 g 3.3 g 2-Methyl-4- [N-ethyl-N- (β-4.5 g 6.0 g hydroxyethyl) amino] aniline sulfate Add water to 10,000 ml 1000 ml pH (25 ℃) 10.05 10.05

Bleach-fix solution Start solution Replenisher Replenisher Fixing agent (see Table 3) 1.3 mol 1.9 mol 1.9 mol Ammonium sulfite 40 g 100 g 100 g (used only when the fixing agent is ammonium thiosulfate) 1,3-propylenediaminetetraacetic acid 2 0.12 mol 0.18 mol 0.18 mol Iron monohydrate chelating agent (same type as bleach) 0.05 mol 0.08 mol 0.08 mol Ammonium bromide 80 g 120 g 150 g Acetic acid 40 g 60 g 65 g Add water 1000 ml 1000 ml 1000 ml pH (25 ° C) ( (Adjust with acetic acid and ammonia) 5.8 5.6 5.4

Rinse water Tap water is washed with H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH-type strong base anion exchange resin (Amberlite IRA-40).
Through a mixed-bed column packed with 0) to reduce the calcium and magnesium ion concentrations to 3 mg / l or less, followed by 20 mg / sodium diisocyanurate dichloride.
Liters and 150 mg / liter of sodium sulfate were added. The pH of this solution was in the range of 6.5 to 7.5.

Stabilizer Starter / Replenisher Common to sodium p-toluenesulfinate 0.1 g Polyoxyethylene-p-monononylphen 0.2 g Nyl ether (average degree of polymerization 10) Disodium ethylenediaminetetraacetate 0.05 g Formalin 0.02 mol Add water 1 liter pH (adjusted with ammonia water and acetic acid) 7.2

[Evaluation of Desilvering Performance] With respect to the black-and-white exposed film before the completion of the running process, the amount of residual silver in the unexposed portion was measured using a fluorescent X-ray analyzer. [Evaluation of Liquid Stability] In addition, the presence or absence of a precipitate in the bleach-fix bath and the washing bath after the running treatment was visually examined. The evaluation was performed based on the following criteria. ：: No precipitation was visually observed Δ: A small amount of precipitation X: A large amount of precipitation The results are shown in Table-3.

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[Table 3]

From Table 3, it can be seen that when the compound of the present invention was used, no precipitation occurred during running processing, the liquid stability was good, and the fixing performance was better than that of thiosulfate. Obtained. This effect is particularly remarkable when the replenishment rate is reduced.

Example 5 Compound-1 of Example 4 was replaced with Compounds-2, 5, 13, 16,
A test similar to that of Example 4 was performed in place of 18, 25, 34, 37 or 44, respectively. As a result, good results were obtained in which the fixing ability was high as in Example 4, and no precipitation occurred during the running process. It was also found that this effect was particularly remarkable when the replenishment was reduced.

Example 6 Using the sample of Example 4, continuous processing (running test) was performed in the following processing steps until the replenishment amount of the fixing solution became twice the tank capacity.

Processing process Temperature Time Replenishment amount ^* Tank capacity (liter) Color development 38.0 ° C 3 minutes 05 seconds 600ml 17 Bleaching 38.0 ° C 1 minute 200ml 5 Set 38.0 ° C 1 minute 20 seconds 400ml 5 or 360ml Rinse with water 38.0 ° C. 30 sec 900 ml 3 stabilization 38.0 ° C. 20 sec - 3 stabilization 38.0 ° C. 20 sec 560 ml 3 drying 80 ° C. 60 seconds * photosensitive material 1 m ² per replenishment rate stabilizing solution is countercurrent system from to. The amount of the developer brought into the bleaching step, the amount of the bleaching liquid brought into the fixing step, and the amount of fixing liquid brought into the washing step are 1 m ² of the photosensitive material.
65 ml and 50 ml, respectively. The crossover time is 6 seconds in each case, and this time is included in the processing time of the previous process. Each replenisher was replenished with the same liquid as the respective tank liquid. The compositions of the bleaching solution and the fixing solution are shown below. The other liquid compositions are the same as in Example 4.

Bleach solution Start solution Replenisher Ferric 1,3-propylenediaminetetraacetate 0.30 mol 0.45 mol ammonium monohydrate ammonium bromide 80 g 120 g ammonium nitrate 15 g 25 g hydroxyacetic acid 50 g 75 g acetic acid 40 g 60 g Liters pH (adjusted with aqueous ammonia) 4.3 4.0

Fixing solution Start solution Replenishing solution Fixing agent 1.3 mol 1.9 mol Ammonium sulfite 40 g 100 g (Used only when the fixing agent is ammonium thiosulfate) Imidazole 17 g 26 g Ethylenediaminetetraacetic acid 13 g 20 g Add water to adjust pH [adjust with ammonia water and acetic acid] 7.0 7.4 The same evaluation as in Example 4 was performed for the desilvering performance and the stability of the fixing solution. The results are shown in Table-4.

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[Table 4]

As can be seen from Table 4, according to the present invention, good results can be obtained in both the desilvering property and the stability of the fixing solution. This effect is particularly remarkable when the replenishment rate is reduced.

Example 7 (1) Preparation of tabular grains Preparation of emulsion 5 g of potassium bromide and 0.1 g of potassium iodide in 1 liter of water.
05 g, gelatin 30 g, thioether HO (CH ₂ ) ₂ S (C
An aqueous solution of 8.33 g of silver nitrate, 5.94 g of potassium bromide, 5.94 g of iodide and 2.5 cc of a 5% aqueous solution of H ₂ ) ₂ S (CH ₂ ) ₂ OH were added to a solution kept at 73 ° C. while stirring. Potassium 0.72
An aqueous solution containing 6 g was added in 45 seconds by the double jet method. Subsequently, after adding 2.5 g of potassium bromide, an aqueous solution containing 8.33 g of silver nitrate was added over 26 minutes so that the flow rate at the end of the addition was twice that at the start of the addition. After this, 20 cc of 25% ammonia solution and 50% N
After 10 cc of H ₄ NO ₃ was added and the mixture was physically aged for 20 minutes, 240 cc of 1N sulfuric acid was added for neutralization. Subsequently, an aqueous solution of 153.34 g of silver nitrate and an aqueous solution of potassium bromide were added to a control solution while maintaining the potential at pAg 8.2.
It was added in 40 minutes by the double jet method. The flow rate at this time was accelerated so that the flow rate at the end of the addition was 9 times the flow rate at the start of the addition. After completion of the addition, 15 cc of a 2N potassium thiocyanate solution was added, and 25 cc of a 1% aqueous solution of potassium iodide was added over 30 seconds. After this the temperature is increased
After removing the soluble salts by the sedimentation method,
The temperature was raised to 0 ° C., 30 g of gelatin and 2 g of phenol were added, and the pH was adjusted to 6.40 by caustic soda and potassium bromide.
Ag was adjusted to 8.10.

After the temperature was raised to 56 ° C., 600 mg of a sensitizing dye having the following structure and 150 mg of a stabilizer were added. 1
0 minutes later, 2.4 mg of sodium thiosulfate pentahydrate, 140 mg of potassium thiocyanate and 2.1 mg of chloroauric acid were added to each emulsion, and after 80 minutes, the emulsion was quenched and solidified to form an emulsion. In the obtained emulsion, 98% of the total projected area of all grains is composed of grains having an aspect ratio of 3 or more, and the average projected area diameter of all grains having an aspect ratio of 2 or more is 1.4.
μm, standard deviation 22%, average thickness 0.187 μm, and aspect ratio 7.5. Sensitizing dye

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Stabilizer

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Preparation of Emulsion Coating Solution A coating solution was prepared by adding the following chemicals per mole of silver halide to the emulsion.・ Gelatin Ag / (gelatin + polymer) ratio (weight) Adjust the amount to be 1.10 ・ Water-soluble polyester 20% (wt% vs. gelatin) ・ Polymer latex (poly (ethyl acrylate / methacrylic acid) = 97/3) 25.0 g Hardener 1,2-bis (vinylsulfonyl 8 mmol / luacetamido) ethane in the emulsion layer of the surface protective layer Per 100 g of gelatin 100 mg of phenoxyethanol 2 g 2,6-bis (hydroxyamino) -4 -Diethylamino-1,3-5-triazine 80 mg-Sodium polyacrylate (average molecular weight 41,000) 4.0 g-Potassium polystyrene sulfonate (average molecular weight 600,000) 1.0 g

Preparation of Photosensitive Material A The coating solution was coated at a thickness of 175 μm simultaneously with the coating solution for the surface protective layer.
On a transparent PET support. The coated silver amount was 3.2 g / m ^{2 on} both sides. The surface protective layer was prepared such that each component had the following coating amount.

Contents of Surface Protective Layer Coating Amount ・ Gelatin 1.15 g / m ²・ Polyacrylamide (average molecular weight 45,000) 0.25 g / m ²・ Sodium polyacrylate (average molecular weight 400,000) 0.02 g / m ² · pt-octylphenoxydiglycerylbutyl sulfonate sodium salt 0.02 g / m ² · poly (degree of polymerization 10) oxyethylene cetyl ether 0.035 g / m ² · poly (degree of polymerization 10) oxyethylene- Poly (degree of polymerization 3) oxyglyceryl p-octylphenoxy ether 0.01 g / m ² .2-Chlorohydroquinone 0.046 g / m ²

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0.003 g / m ²

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0.001 g / m ²

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0.003 g / m ² .proxel 0.001 g / m ² .polymethyl methacrylate (average particle size 3.5 μm) 0.025 g / m ² .poly (methyl methacrylate / methacrylate) (molar ratio 7: 3, Average particle size 2.5 μm) 0.020 g / m ²

(2) Preparation of potato-like particles Preparation of emulsion 20 g of gelatin, 30 g of potassium bromide in 900 cc of water,
3.91 g of potassium iodide was added, and silver nitrate was added in the form of an aqueous solution over 35 minutes while stirring in a vessel maintained at 48 ° C.
g was added. Further, ammoniacal silver nitrate (165 g as silver nitrate) was added simultaneously with the aqueous potassium bromide solution by the double jet method over 5 minutes. After the addition,
After removing soluble salts at 35 ° C. by sedimentation,
The temperature was raised to 0 ° C., and 100 g of gelatin was added to adjust the pH to 6.7.
Was adjusted. The resulting emulsion has a potato-like shape, and the average diameter of a sphere having the same volume as each particle is 0.1 mm.
At 82 μm, the silver iodide content was 2 mol%. This emulsion was subjected to chemical sensitization using gold and sulfur sensitization together.

Preparation of Photosensitive Material B In addition to gelatin, an average molecular weight of 8000 was used as a surface protective layer.
Polyacrylamide, polystyrene sodium sulfonate,
Polymethyl methacrylate fine particles (average particle size 3.
0 μm), an aqueous gelatin solution containing polyethylene oxide, a hardener and the like. Anhydro-5,5'-dichloro-9- as a sensitizing dye in each of the above emulsions
500 mg of ethyl-3,3'-di (sulfopropyl) oxacarbocyanine hydroxide sodium salt
/ Mol Ag at a rate of 200 mg / mol A
g. Further, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene and 2,6-bis (hydroxyamino) -4-diethylamino-1,3,5-triazine and nitrone as stabilizers are dried. A light-sensitive material B was prepared by adding trimethylolpropane, a coating aid, and a hardening agent as an antifoggant to form a coating solution, and coating and drying the both sides of the polyethylene terephthalate support simultaneously with the surface protective layer. The coated silver amount of this light-sensitive material was 6.4 g / m ² in total on both sides.

Development Preparation of Concentrate <Developer> Part A Potassium hydroxide 330 g Potassium sulfite 630 g Sodium sulfite 240 g Potassium carbonate 90 g Boric acid 45 g Diethylene glycol 180 g Diethylenetriaminepentaacetic acid 30 g 1- (Diethylaminoethyl) -5-mercaptotetrazole 75 g Hydroquinone 450 g Add water 4125 ml Part B Diethylene glycol 525 g Glacial acetic acid 102.6 g 5-Nitroindazole 3.75 g 1-phenyl-3-pyrazolidone 34.5 g Add water 750 ml Part C Glutaraldehyde (50 wt / wt%) 150 g Meta Potassium bisulfite 150 g Potassium bromide 15 g Add water 750 ml

<Fixing Solution> Ammonium thiosulfate (70 wt / vol%) or the fixing agent of the present invention 1.0 mol ethylenediaminetetraacetic acid disodium dihydrate 0.03 g sodium sulfite (only when ammonium thiosulfate is used) 20 g Acid 4 g 1- (N, N-dimethylamino) -ethyl-5-mercaptotetrazole 1 g Tartaric acid 3.2 g Glacial acetic acid 45 g Sodium hydroxide 15 g Sulfuric acid (36 N) 3.9 g Aluminum sulfate 10 g Add water 400 ml pH 4. 68

Preparation of Processing Solution The above concentrated developer solution was filled into polyethylene containers for each part. This container is one in which the containers of parts A, B, and C are connected together. In addition, the above fixer concentrate was also filled in a polyethylene container. After the above-mentioned concentrated solution of the developer was prepared, it was stored in a container at 50 ° C. for 3 months, and then used for preparing the developer. The developing solution and the fixing solution were filled in the developing tank and the fixing tank of the automatic processing machine at the following ratios using the metering pumps respectively installed in the automatic processing machine.

Developer (pH 10.50) 55 ml of Part A, 10 ml of Part B, 10 parts of Part C
Was mixed with 10 ml of water and 125 ml of water. Fixer (pH 4.65) 80 ml of the concentrated solution and 120 ml of water were mixed to prepare a solution. Fill the flushing tank with tap water and place Na ₂ O / B on the bottom of the tank.
Silver release agent 50 containing 1.7 wt% of Ag ₂ O in a fusing glass made of ₂ O ₅ / SiO ₂ (ratio of 10/65/25 wt%)
g were wrapped in a nonwoven fabric and four bags were sunk.

After cutting the photosensitive materials A and B, X-ray exposure was given by 50%, and continuous processing was performed using an automatic developing machine until the replenishment amount of the fixing solution was twice the tank capacity in the following processing step. (Running test).

Processing step Temperature Time Replenishment amount ^* Tank capacity (liter) Current image 35 ° C 13.3 seconds 45ml 15 Fix 32 ° C 10.5 seconds 30ml 15 or 20ml Rinsing 18 ° C 5.7 seconds 13 * 4 Cutting size (10 x 12 inches) Quantity per sheet Rinse water is 5 liters per minute for processing and 10 liters per minute for processing, and is synchronized with the time when the photosensitive material is being processed. The solenoid valve is opened and supplied (about 1
At the end of the day's work, the solenoid valve was automatically opened to drain all water from the tank. The crossover roller between development and fixing and between fixing and washing was equipped with a device for automatically applying washing water for washing (method described in Japanese Patent Application No. 61-131338).

[Evaluation of Desilvering Performance] With respect to the processed film before the completion of the running process, the amount of residual silver in the unexposed portion was measured using a fluorescent X-ray analyzer. [Evaluation of Solution Stability] The presence or absence of a precipitate in the fixing bath after the running treatment was visually examined. The evaluation was made based on the following criteria. ：: no precipitation by visual inspection △: small amount of precipitation ×: large amount of precipitation

The results are shown in Tables 5 and 6.

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[Table 5]

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[Table 6]

As can be seen from Tables 5 and 6, when the compound of the present invention was used, no precipitate was formed even during the running process, the solution stability was good, and the fixing performance was superior to that of thiosulfate. It can be seen that good results were obtained. This effect is particularly remarkable when the replenishment rate is reduced.

Example 8 Compound-1 of Example 7 was replaced with Compounds-2, 6, 14, 16,
A test similar to that of Example 7 was performed in place of 19, 26, 37, 39 or 44, respectively. As a result, as in Example 7, good results were obtained in which the fixing ability was high and no precipitation occurred during the running process. It was also found that this effect was particularly remarkable when the replenishment was reduced.

Example 9 Silver halide grains were precipitated by a double jet method.
After physical ripening and desalting, it is further chemically ripened and silver chloroiodobromide (bromine content: 30 mol%, iodine content: 0.1 mol%)
An emulsion was obtained. The average diameter of silver halide grains contained in this emulsion was 0.3 μm. 0.6 kg of silver halide was contained in 1 kg of this emulsion. This emulsion is
Kg was weighed out and dissolved by heating at 40 ° C., and 70 ml of a 0.05% by weight methanol solution of sensitizing dye (9-1) shown below was dissolved.
And a predetermined amount of an aqueous solution of sodium bromide. Next, 25 ml of a 1.0% by weight methanol solution of the compound (9-2) and 50 ml of a 0.5% by weight methanol solution of the compound (9-3) were added.
30 ml of a 1.0% by weight aqueous solution of 5-dichlorotriazine sodium salt was added, and 40 ml of a 1.0% by weight aqueous solution of dodecylbenzenesulfonic acid sodium salt were further added and stirred. This finished emulsion was coated on a cellulose triacetate film base so as to have a dry film thickness of 5 μm and dried to obtain a sample of a light-sensitive material.

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After cutting the thus-prepared sample, black-and-white exposure was performed, and the replenishment amount of the fixing solution was reduced in the following processing steps.
Continuous processing (running test) was performed until the tank capacity was doubled.

Processing process Step Processing time Processing temperature Replenishment amount Tank capacity (liter) Current image 20 seconds 38 ° C. 320 ml 18 Fixation 12 seconds 38 ° C. 300 ml 18 200 ml Rinsing 20 seconds 20 ° C. 2 l 18 The replenishing amount is photosensitive. is the amount per material 1 m ^2.

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[Table 7]

[Evaluation of Desilvering Performance] For the processed film before the completion of the running process, the amount of residual silver in the unexposed area was measured using a fluorescent X-ray analyzer. [Evaluation of Solution Stability] The presence or absence of a precipitate in the fixing bath after the running treatment was visually examined. The evaluation was made based on the following criteria. ：: No precipitation was observed visually Δ: A small amount of precipitation ×: A large amount of precipitation The results are shown in Table-8.

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[Table 8]

From Table 8, it can be seen that when the compound of the present invention was used, no precipitation occurred during the running process, the liquid stability was good, and the fixing performance was better than that of thiosulfate. It can be seen that it was obtained. This effect is particularly remarkable when the replenishment rate is reduced.

Example 10 Compound-2 of Example 9 was replaced with Compound-4, 5,10,17 ,
Example 9 in place of 25, 34, 39 or 44, respectively
The same test was performed. As a result, good results were obtained in which the fixing ability was high as in Example 9 and no precipitation occurred during the running process. It was also found that this effect was particularly remarkable when the replenishment was reduced.

[0204]

According to the present invention, there is an excellent effect that the stability of the processing solution is high even with low replenishment. The processability is excellent even when the color photographic material is subjected to the fixing process or the bleach-fixing process of the present invention under the condition of low replenishment. That is, according to the method of the present invention, a mercapto compound represented by the general formula (I) having a cation group and an anion group in one molecule simultaneously and / or a meso-ion thiolate having a cation group and an anion group simultaneously in one molecule By using the compound as a processing solution having a fixing ability, a solution having a stable fixing ability and good de-Ag property can be obtained. In addition, when the compound is used in a color developing solution, a good antifogging effect can be obtained. Can be

Continuation of front page (56) References JP-A-64-4739 (JP, A) JP-A-2-44355 (JP, A) JP-A-2-232654 (JP, A) JP-A 64-73344 (JP) , A) (58) Field surveyed (Int. Cl. ⁷ , DB name) G03C 7/42 G03C 7/407 G03C 5/26

Claims (4)

(57) [Claims] 1. A post-exposure of the silver halide photographic material having at least one light-sensitive silver halide emulsion layer on a support, in the processing method for development processing, low in one molecule
At least one cationic group and at least one anionic group
At least one selected from a mercapto compound represented by the following general formula (I) and a meso-ion thiolate compound having at least one cation group and at least one anion group in a molecule simultaneously as substituents. A method for processing a silver halide photographic material, characterized by processing with a processing solution containing a compound. General formula (I) (In the formula, Q represents an atomic group necessary for forming a tetrazole ring, a triazole ring, an imidazole ring or an oxadiazole ring. This heterocycle may be condensed with a carbon aromatic ring or a heteroaromatic ring. R represents an alkyl group, an alkenyl group, an aralkyl group, an aryl group or a heterocyclic group, n represents an integer of 1 to 4, and M represents a counter cation, provided that at least one of Rs is a cationic group or an anionic group. Shall be replaced by at least one of 2. A processing method for exposing and developing a silver halide photographic material having at least one photosensitive silver halide emulsion layer on a support , wherein at least one bath having a fixing ability is present in one molecule. Two cationic groups and at least
Also, from a mercapto compound represented by the following general formula (I) having one anionic group as a substituent at the same time and a meso-ion thiolate compound having at least one cationic group and at least one anionic group as a substituent in one molecule simultaneously A method for processing a silver halide photographic material, characterized by containing at least one selected compound. General formula (I) (In the formula, Q represents an atomic group necessary for forming a tetrazole ring, a triazole ring, an imidazole ring or an oxadiazole ring. This heterocycle may be condensed with a carbon aromatic ring or a heteroaromatic ring. R represents an alkyl group, an alkenyl group, an aralkyl group, an aryl group or a heterocyclic group, n represents an integer of 1 to 4, and M represents a counter cation, provided that at least one of Rs is a cationic group or an anionic group. Shall be replaced by at least one of 3. At least one cationic group in one molecule
And at least one anionic group simultaneously as a substituent
Contain at least one compound selected from the meso-ionic thiolate compound having at least one cationic group and at least one anionic group as a simultaneous substituent mercapto compound and in one molecule represented by the following general formula (I) to A photographic fixing composition comprising: General formula (I) (In the formula, Q represents an atomic group necessary for forming a tetrazole ring, a triazole ring, an imidazole ring or an oxadiazole ring. This heterocycle may be condensed with a carbon aromatic ring or a heteroaromatic ring. R represents an alkyl group, an alkenyl group, an aralkyl group, an aryl group or a heterocyclic group, n represents an integer of 1 to 4, and M represents a counter cation, provided that at least one of Rs is a cationic group or an anionic group. Shall be replaced by at least one of Wherein at least one organic <br/> be Rume source ion thiolate compounds as simultaneously substituent at least one anionic group and the cationic group is represented by the general formula (II) compound in a molecule 2. A method for processing a silver halide photographic light-sensitive material according to claim 1, wherein: General formula (II) (In the formula, Z represents an atomic group necessary to form a 5- or 6-membered mesoionic ring. Further, this heterocyclic ring may be condensed with a carbon aromatic ring or a heteroaromatic ring. (It has the same meaning as that of (I). M represents an integer of 1 to 3.)